CN103143348B - A kind of preparation method of the Pd@Pt fuel-cell catalyst for direct methanoic acid fuel cell - Google Patents

A kind of preparation method of the Pd@Pt fuel-cell catalyst for direct methanoic acid fuel cell Download PDF

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CN103143348B
CN103143348B CN201310060299.5A CN201310060299A CN103143348B CN 103143348 B CN103143348 B CN 103143348B CN 201310060299 A CN201310060299 A CN 201310060299A CN 103143348 B CN103143348 B CN 103143348B
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fuel
preparation
suspension
carrier
obtains
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CN103143348A (en
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邢巍
司凤占
刘长鹏
廖建辉
梁亮
李晨阳
张玉微
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

Carrier a) in deionized water, is obtained mixed solution by alternately ultrasonic, dispersed with stirring by the preparation method that the invention provides a kind of Pd@Pt fuel-cell catalyst for direct methanoic acid fuel cell; B) add the aqueous solution of Pd precursor and reducing agent in the mixed solution obtained to step a), use immersion reduction method to carry out load and the reduction of Pd nano particle, obtain the carrier suspension after load P d; C) haloid and Pt precursor are added in the suspension that step b) obtains, stir lower heating, displacement reaction occurs; D) deionized water is used to wash away Cl in the suspension that step c) obtains -, after filtration drying, obtain Pd@Pt fuel-cell catalyst.Preparation method provided by the invention does not use surfactant and masterplate, realizes noble metal nano particles surface controlled, simple to operate.

Description

A kind of preparation method of the Pd@Pt fuel-cell catalyst for direct methanoic acid fuel cell
Technical field
The present invention relates to dye cell technical field, particularly relate to a kind of preparation method of the Pd@Pt fuel-cell catalyst for direct methanoic acid fuel cell.
Background technology
Direct methanoic acid fuel cell replaces hydrogen as the fuel cell that can contaminate source using liquid formic.Because oxidation current is high, self ionizable solution of leading is electrically excellent, and film permeability is little, direct methanoic acid fuel cell has very large potentiality in the power supply as automobile and portable electron device, and direct formic acid dye cell is primarily of anode and dyestuff, and negative electrode composition.Anode the most frequently used is at present Pd base electrode, but when electroxidation formic acid, simple Pd electrode can slowly dissolve, and can generate CO and can poison Pd, and reduce catalyst persistence, cause the utilization rate of Pd lower, this causes the lifting of battery cost simultaneously.
At present, the report being much directed to and improving the catalyst based durability of Pd has been had.Wherein, by modifying carrier or meeting carrier, and Pd alloy improves the catalyst based CO tolerance catalysts performance of Pd and durability is common method.But this method is all not ideal enough for the loss control effect of doping composition and Pd, unfavorable to electro-catalysis.
What be usually used in formic acid anode catalyst also has Pt, and corrosion resistance is better, but, the poor catalytic activity of Pt.So the nucleocapsid structure designing a kind of Pd@Pt is a possible outlet of formic acid electro-oxidizing-catalyzing agent.Xia etc. obtain different nanostructured (referring to H.Zhang by adopting the crystal face-selective epitaxial growth of Pd nanocube template and haloid control Pt, M.Jin, J.Wang, W.Li, P.H.C.Camargo, M.J.Kim, D.Yang, Z.Xie, Y.Xia, Journal of theAmerican Chemical Society, 133 (2011) 6078-6089.) but, this meticulous nanometer construction method is not easily applied to the synthesis of large-scale catalyst and produces.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of the Pd@Pt fuel-cell catalyst for direct methanoic acid fuel cell not use surfactant and masterplate, realizes noble metal nano particles surface controlled, simple to operate.
In order to solve above technical problem, the invention provides a kind of preparation method of the Pd@Pt electrode for direct methanoic acid fuel cell, comprising:
A) carrier in deionized water, is obtained mixed solution by alternately ultrasonic, dispersed with stirring;
B) add the aqueous solution of Pd precursor and reducing agent in mixed solution a) obtained to step, use immersion reduction method to carry out load and the reduction of Pd nano particle, obtain the carrier suspension after load P d;
C) haloid and Pt precursor are added step b) in the suspension that obtains, stir lower heating, displacement reaction occurs;
D) deionized water is used to wash away step c) Cl in the suspension that obtains -, after filtration drying, obtain Pd@Pt fuel-cell catalyst.
Preferably, described carrier is selected from one or more in active carbon, CNT, Graphene and titanium dioxide.
Preferably, described Pd precursor is PdCl 2acidic aqueous solution.
Preferably, described reducing agent is hydroboron.
Preferably, described Pt precursor is H 2ptCl 6the aqueous solution.
Preferably, steps d) be specially:
D1) the deionized water filtering and washing step c that uses resistivity to be 18.2M Ω cm) suspension that obtains is to without Cl --exist;
D2) insoluble matter obtained by suction filtration vacuum drying at 80 DEG C, obtains Pd@Pt electricity fuel cell catalyst.
Preferably, step a) in described carrier be active carbon, CNT, Graphene or TiO 2.
Present invention also offers a kind of fuel cell electrode, comprise glass-carbon electrode, and be coated on Pd@Pt fuel-cell catalyst prepared by described claim 1 method.
The invention provides a kind of preparation method of the Pd@Pt fuel-cell catalyst for direct methanoic acid fuel cell, adopt the selective absorption of halide ion, reduce in a heated condition, to reach the object of control Pt atom in Pd surface deposition state.Adopt halide ion absorption crystal face-selective, and then controls Pt deposits, and ensures the surperficial different conditions of the nucleocapsid structure of gained.The present invention proposes a kind of halide ion that adopts to control, in the synthetic method of Pd surface coverage degree, do not use surfactant and template by Pt in displacement reaction control Pd@Pt structure between Pd, Pt.Utilize the selective absorption of halide ion, reduce in a heated condition, to realize Pt atom in the controlled object of Pd surface deposition state.It is controlled that this preparation method achieves noble metal nano particles surface, and operation is comparatively easy, is applicable to expanding synthesis scale, for commercializing fuel cells provide a kind of can the preparation method of batch duplicating.
Accompanying drawing explanation
Fig. 1 prepares the XRD curve that carbon carries Pd-Pt catalyst under different condition;
Fig. 2 is the cyclic voltammetry curve of different carbon supported catalyst in sulfuric acid solution;
Fig. 3 is the cyclic voltammetry curve of catalyst in sulfuric acid solution in comparative example;
Fig. 4 is the cyclic voltammetry curve of catalyst in sulfuric acid solution in embodiment 1;
Fig. 5 is the cyclic voltammetry curve of catalyst in sulfuric acid solution in embodiment 2;
Fig. 6 is the cyclic voltammetry curve of catalyst in sulfuric acid solution in embodiment 3;
Fig. 7 is the cyclic voltammetry curve of different carbon supported catalyst in sulfuric acid-formic acid solution;
Fig. 8 is the chronoa mperometric plot of different carbon supported catalyst in sulfuric acid-formic acid solution.
Detailed description of the invention
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these describe just as further illustrating the features and advantages of the present invention instead of the restriction to patent requirements of the present invention.The invention provides a kind of preparation method of the Pd@Pt fuel-cell catalyst for direct methanoic acid fuel cell, comprising:
A) carrier in deionized water, is obtained mixed solution by alternately ultrasonic, dispersed with stirring;
B) add the aqueous solution of Pd precursor and reducing agent in mixed solution a) obtained to step, use immersion reduction method to carry out load and the reduction of Pd nano particle, obtain the carrier suspension after load P d;
C) haloid and Pt precursor are added step b) in the suspension that obtains, stir lower heating, displacement reaction occurs;
D) deionized water is used to wash away step c) Cl in the suspension that obtains-, after filtration drying, obtain Pd@Pt fuel-cell catalyst.
According to the present invention, first pass through alternately ultrasonic by carrier, dispersed with stirring, in deionized water, obtains mixed solution, and wherein said carrier is preferably the carbon carriers such as active carbon, CNT, Graphene, also can be TiO 2deng fuel cell common carrier, be more preferably active carbon, CNT, Graphene or TiO 2and by ultrasonic disperse in deionized water.
Then add the aqueous solution of Pd presoma and reducing agent in mixed solution a) obtained to step, use immersion reduction method to carry out load and the reduction of Pd nano particle, obtain the carrier suspension after load P d.Wherein said Pd presoma is preferably PdCl 2acidic aqueous solution, described reducing agent is the reducing agent being preferably applicable to immersion reduction method under normal temperature, is more preferably NaBH 4.Described Pd presoma and described reducing agent mass ratio are: (1 ~ 3): (1 ~ 10).Be more preferably 1:(8 ~ 10).According to the present invention, described carrier can add arbitrarily relative to Pd presoma.Be preferably (10 ~ 20): 1.
Haloid and Pt presoma are added step b) suspension that obtains, under agitation heat, displacement reaction occurs, in displacement reaction process, Pt and the Pd be reduced carries out reaction and starts to form Pd@Pt fuel-cell catalyst.Wherein said Pt precursor is preferably H 2ptCl 6the aqueous solution, the temperature of described heating is preferably 85 ~ 100 DEG C, obtains the Pd@Pt/C with nucleocapsid structure after displacement reaction.Described haloid selects cation that the halogen compounds be hydrolyzed does not occur, and be more preferably KCl or KBr, used is anion, and cation is not hydrolyzed
Use deionized water washing step c) in chlorion Cl -, the concrete steps of washing are:
D1) the deionized water filtering and washing step c that uses resistivity to be 18.2M Ω cm) suspension that obtains is to without Cl --exist;
D2) insoluble matter obtained by suction filtration vacuum drying at 80 DEG C, obtains Pd@Pt fuel-cell catalyst.
The present invention adds AgNO preferably by filtrate 3solution, occurs detecting whether have Cl without precipitation --exist.
In the present invention, adopt the selective absorption of halide ion, reduce in a heated condition, to reach the object of control Pt atom in Pd surface deposition state.Adopt the crystal face-selective of halide ion absorption, and then control Pt deposits, and ensure the nucleocapsid structure surface different conditions of gained.
Employing halide ion controls, by Pt in displacement reaction control Pd@Pt structure between Pd, Pt in the synthetic method of Pd surface coverage degree.The method comprises dispersible carrier, reducing loaded Pd nano particle, displacement reaction and follow-up washing dries four steps; Add a certain amount of carbon carrier and deionized water in dispersible carrier step step, and obtain disperseing sufficient carbon carrier suspension by stirring alternately and ultrasonic process; Easy immersion reduction method is adopted in reducing loaded Pd nano particle step; In displacement reaction step, haloid control Pt is adopted to deposit at Pd nano particle; Adopt deionized water filtering and washing to cause at water-washing step and can't detect Cl -, dry 12h for 80 DEG C afterwards.This synthetic method successfully achieves the synthesis of the controlled Pd@Pt fuel-cell catalyst of surface composition, and controllability is good, need not surfactant and template, is easy to the process such as follow-up washing.As long as control halogen kind, addition can control carrying capacity, control urea addition and can control particle diameter.
Be below the specific embodiment of the invention, elaborate the present invention program.
Embodiment 1:
First prepare the content 20wt%Pd/C of Pd, adopt U.S. CABOT Cabot carrier Vulcan XC-72R.Wherein the parameter of carrier is:
The parameter of table 1 carrier
Model VXC-72
Physical aspect Powdery
Specific area 254
DBP oil factor (cc/100g) 192
Particle diameter (nm) 30
Tinting strength, tinting power (ASTM) 87
Density (g/l) 96.1
First by 80mg carrier, by 0.5h ultrasonic disperse in 200mL deionized water.Add precursor PdCl again 2aq (4mg pd/ mL, HCl 5M), again by 0.5h ultrasonic disperse.Use NaOH concentrated solution to regulate its pH to 10, dropwise add NaBH 4solution (NaBH 480mg/ deionized water 50mL) reduce precursor.Reduce laggard line replacement step: in the above-mentioned Pd presoma be reduced, add H 2ptCl 6solution (18.105mg pt/ mL) and KCl 0.045g, 90 DEG C of stirring in water bath 12h.Wash the deionized water of deionization step use resistivity 18.2M Ω cm, filtering and washing extremely without Cl -exist and (in filtrate, add AgNO 3solution, occurs without precipitation), finally vacuum drying at 80 DEG C.Numbering c.
Carry out XRD test, scanning angle 10 ° ~ 90 ° by after above-mentioned catalyst fines grinding, sweep speed 5 °/min, Fig. 1.
Get this catalyst 5mg and add 50 μ L Nafion solution (Aldrich, 5wt%Nafion) ultrasonic disperse 30min, get 10 these inks of μ L, drip and be applied to glass-carbon electrode, room temperature is dried, and makes membrane electrode.Use SCE electrode as to electrode, utilizes three-electrode system, at the 0.5M H of nitrogen deoxygenation as reference electrode, Pt sheet 2sO 4cyclic voltammetry curve in solution, sweeps speed for 20mV/s.Acquired results, as Fig. 2, by integral and calculating comparative example electrochemical surface area (table 2).Comparative example 2,3 and comparative example, can find out that the introducing of displacement step makes H adsorption desorption area increase 50%, and this can ascribe the change that the deposition of Pt atom and Pd nanoparticle surface produce due to displacement to.
In above-mentioned solution, carry out the experiment of CO adsorption desorption, choose after double-deck district current potential leads to CO gas 15min and use high-purity N 2go out CO in solution, carry out cyclic voltammetric 2 and enclose, as Fig. 5.Comparative example 2,3 and comparative example, can find out that the introducing of displacement step is little for the impact of CO adsorption capacity, but make CO oxidation peak that negative moving occur, and poisons species more easily oxidized namely.
At the 0.5M H of nitrogen deoxygenation 2sO 4the results are shown in Figure 7 with the cyclic voltammetry that 0.5M HCOOH solution carries out.Comparative example 2,3 and comparative example, can find out and introduce the peak shape that the sample that obtains of displacement step has obvious Pt catalysis Oxidation of Formic Acid, and the one group of first step peak adding KCl is higher.
Chrono-amperometric test is carried out in this solution, Fig. 8 with 0.3V current potential.Can find out that the sample electro-chemical activity that embodiment 1 obtains declines less in time.
Embodiment 2: sample preparation methods is basic identical with embodiment 1, and difference is to change KCl into KBr 0.060g.Method of testing is identical with embodiment 1,0.5M H 2sO 4cyclic voltammetry curve in solution is if the experiment of Fig. 2, CO adsorption desorption is as Fig. 6,0.5M H 2sO 4the cyclic voltammetry carried out with 0.5M HCOOH solution and chrono-amperometric test result are shown in Fig. 7 and Fig. 8.
Embodiment 3: sample preparation methods is basic identical with embodiment 1, and difference is not add KCl.Method of testing is identical with embodiment 1,0.5M H 2sO 4cyclic voltammetry curve in solution is if the experiment of Fig. 2, CO adsorption desorption is as Fig. 4,0.5M H 2sO 4the cyclic voltammetry carried out with 0.5M HCOOH solution and chrono-amperometric test result are shown in Fig. 7 and Fig. 8.
Comparative example: sample preparation methods is basic identical with embodiment 1, and difference is to add NaBH 4directly carry out washing step afterwards.Method of testing is identical with embodiment 1,0.5M H 2sO 4cyclic voltammetry curve in solution is if the experiment of Fig. 2, CO adsorption desorption is as Fig. 3,0.5M H 2sO 4the cyclic voltammetry carried out with 0.5M HCOOH solution and chrono-amperometric test result are shown in Fig. 7 and Fig. 8.Experimental result is as shown in table 2.
Table 2 electrochemical active surface and CO electroxidation spike potential (Fig. 2 ~ 6)
Above the preparation method of a kind of Pd@Pt fuel-cell catalyst for direct methanoic acid fuel cell provided by the invention is described in detail, apply specific case herein to set forth principle of the present invention and embodiment, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping, should be understood that, for those skilled in the art, under the premise without departing from the principles of the invention, some improvement and modification can also be carried out to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.

Claims (5)

1., for a preparation method for the Pd Pt fuel-cell catalyst of direct methanoic acid fuel cell, it is characterized in that, comprising:
A) carrier in deionized water, is obtained mixed solution by alternately ultrasonic, dispersed with stirring, described carrier be selected from active carbon, CNT, Graphene and titanium dioxide one or more;
B) add the aqueous solution of Pd precursor and reducing agent in mixed solution a) obtained to step, use immersion reduction method to carry out load and the reduction of Pd nano particle, obtain the carrier suspension after load P d,
Described reducing agent is hydroboron;
C) haloid and Pt precursor are added step b) in the suspension that obtains, stir lower heating, displacement reaction occurs,
Described Pt precursor is H 2ptCl 6the aqueous solution;
Described haloid is the halogen compounds that cation does not occur to be hydrolyzed;
D) deionized water is used to wash away step c) Cl in the suspension that obtains ~, after filtration drying, obtain Pd@Pt fuel-cell catalyst.
2. preparation method according to claim 1, is characterized in that, described Pd precursor is PdCl 2acidic aqueous solution.
3. preparation method according to claim 1, is characterized in that, steps d) be specially:
D1) the deionized water filtering and washing step c that uses resistivity to be 18.2M Ω cm) suspension that obtains is to without Cl --exist;
D2) insoluble matter obtained by suction filtration vacuum drying at 80 DEG C, obtains Pd@Pt fuel-cell catalyst.
4. preparation method according to claim 1, is characterized in that, step a) in described carrier be active carbon, CNT, Graphene or TiO 2.
5. a fuel cell electrode, is characterized in that, comprises glass-carbon electrode, and Pd Pt fuel-cell catalyst prepared by coating described claim 1 method thereon.
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